This invention relates to an improved method for preparing light-absorbing polymeric compositions, which are useful as powders or pellets for incorporation into a variety of thermoplastic resins such as cellulose esters, polyesters, polyolefins, polycarbonates, polyamides, etc. by conventional melt or solution blending techniques. The colored thermoplastic resins thus produced have good clarity, good color development, excellent fastness to light and are useful for a variety of end uses where nonhazardous, nonmigrating, or nonextractable colorants are needed.
It is well-known that thermoplastic polymers may be colored by adding pigments or solvent dyes (e.g., see Thomas G. Weber, Editor, Coloring of Plastics, John Wiley and Sons, New York, 1979). The use of pigments, however, is accompanied by undesirable properties such as opacity, dullness of color, low tintorial strength, etc. Also, difficulties in uniformly blending the insoluble pigments with the thermoplastic resin are often encountered. Also useful for coloring thermoplastic polymers are the solvent dyes (K. Venkataraman, Editor, The Chemistry of Synthetic Dyes, Vol. 8, Academic Press, New York, 1978, pp. 81-131), which provide compositions having improved clarity, brightness in hue and high tinctorial strength, but which may lead to dye migration, extraction, etc. from the colored thermoplastic polymer. These problems are of particular concern when solvent dyes are used to color flexible polymers such as polyvinyl chloride, polyethylene and polypropylene which have low glass transition temperatures.
Plastics, paints, printing inks, rubber, cosmetics, and similar materials are typically colored by organic pigments when superior brilliance and tinctorial strength are important. Toxicity considerations have presented chronic problems relative to the use of organic pigments since some have been shown to be potential carcinogens and to cause contact dermatitis.
Plastics are also colored by using color concentrates consisting of physical admixtures of polymers and colorants (usually solvent dyes). However, the use of such physical admixtures to color polymeric materials such as polyester, e.g., poly(ethylene terephthalate) and blends thereof, present a number of problems, including:
Colorant migration during drying of the colored polyester pellets.
Colorant migration during extrusion and colorant accumulation on dies which can cause shutdowns for clean-up. Such colorant migration and accumulation result in time consuming and difficult clean-up, particularly when a polymer of another color is subsequently processed on the same equipment.
Colorants may not mix well, for example, when using two or more color cencentrates to obtain a particular shade.
Colorants may diffuse or exude during storage and use of the colored polymeric material.
The colored polymeric compositions which are prepared by the process of this invention eliminate or minimize the aforementioned problems associated with the use of conventional dyes and pigments.
To attempt to overcome some of the problems mentioned above, particularly as relates to coloring polyesters, colored polyester compositions have been prepared by copolymerizing relatively low amounts of monomeric colorants during the polymer preparation (U.S. Pat. Nos. 5,194,571; 5,106,942; 5,102,980; 5,032,670; 4,892,922; 4,740,581; 4,403,092; 4,359,570; 4,267,306 and W092/07913). However, the preparation of these colored polymers require dyes having outstanding thermal stability since the colorants are exposed to very high temperatures for prolonged periods of time necessary for polyester formation, thus severely circumscribing the selection of efficacious colorants. For example, only the nonazo type colorants have been shown to have the adequate thermal stability for copolymerization into polyesters, since azo type compounds do not have the resquite thermal stability for copolymerization.
Furthermore, it is known to prepare polymeric dyes by reacting dyes containing reactive hydroxy and amino groups with organic di-acid chlorides in solvents (U.S. Pat. Nos. 2,994,693; 3,403,200; 4,619,990; 4,778,742; 5,401,612). Although this method of polymer preparation allows the use of a wide range of chromophoric classes, including azo compounds, as colorant monomers, the polymerization reaction in each case involves the use of very reactive organic di-acid chlorides which are toxic and involve difficult to handle inorganic halogen compounds in their preparation and have accompanying problems of hydrolysis in the presence of water which causes serious handling and storage problems. The hydrolysis product (HCl) is particularly corrosive and makes storage of these compounds difficult. Furthermore, since the di-acid chlorides will react with water, the monomeric dyes must be specially dried to avoid side reactions in the polymer preparation.
In a similar attempt to prepare polymeric dyes using relatively low temperatures, polyurethanes have been prepared by reacting dyes bearing two hydroxyalkyl group with aliphatic and aromatic isocyanates (U.S. Pat. No. 5,194,463). However, the organic isocyanates themselves are extremely toxic and present difficult handling problems. They also are reactive with water and thus the reaction requires specially dried monomeric dyes. Also, the colored polyurethanes as a class do not have excellent thermal stability.
It is further known to prepare colored condensation polymers by reacting a polymerizable lactone or a hydroxyalkanoic acid with a dye containing reactive hydroxy group (U.S. Pat. No. 4,933,426). The procedure again requires relatively high reaction temperatures and prolonged times and use a large excess of the lactone reactant. The method is further hindered by the fact that some lactones are suspected carcinogens.
Light-absorbing polymeric compositions have also been produced by free radical polymerization of vinyl functionalized light-absorbing monomers (U.S. Pat. Nos. 5,310,837; 5,334,710; 5,359,008; 5,434,231 and 5,461,131).
Finally, it is known that one may color plastics, in particular polyolefins, with low melting, cross-linked colored polyester compositions containing residues of terephthalic acid, isophthalic acid, or both, a low-molecular weight trimethylol alkane, i.e., 1,1,1-trimethylol propane and a copolymerizable colorant, said colorant being present at a level of 0.1-25% by weight (U.S. Pat. No. 4,116,923). Difficulties are encountered, however, in preparing these highly cross-linked colored polymers as extreme care with regard to the temperature, amount of vacuum, the level of colorant present, and the reaction time, is necessary in order to attempt to reproduce the same quality of cross-linked colored polyester composition. Further, these colored polyester compositions are brittle or low melting and may cause deterioration in physical properties of themoplastic polymers when added in quantities sufficient to produce a high level of coloration.
This invention relates to a method for preparing a light absorbing linear polymeric having Formula I 
wherein A comprises the residue of a diacidic monomer comprising about 1 to 100 mole % of at least one light-absorbing monomer having a light absorption maximum between about 300 nm and about 1200 nm and wherein the remaining portion of A comprises the residue of a non-light absorbing monomer which does not absorb significantly at wavelengths above 300 nm or has a light absorption maximum below 300 nm and wherein B is a divalent organic radical selected from C2-C12 alkylene, C3-C8 cycloalkylene, C1-C4 alkylene-C3-C8-cycloalkylene-C1-C4 alkylene, C1-C4 alkylene-arylene-C1-C4 alkylene, C2-C4 alkylene-Oxe2x80x94C2-C4 alkylene, and C2-C4-alkylene-L-arylene-C2-C4 alkylene and C2-C4 alkylene-(L-C2-C4 alkylene)1-4, wherein L is a linking group selected fromxe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94N(C1-C6 alkyl)-, xe2x80x94N(aryl)-, xe2x80x94N(SO2 C1-C6 alkyl)-, xe2x80x94N(SO2aryl)-, xe2x80x94SO2N(C1-C6 alkyl)- and combinations thereof; wherein n is at least 2.
The process comprises reacting said diacidic monomer with an organic compound of Formula II
Xxe2x80x94Bxe2x80x94X1xe2x80x83xe2x80x83II
wherein B is as defined above and X and X1 reactive groups and are independently selected from bromine, iodine and Rxe2x80x94SO2O; wherein R is selected from C1-C6 alkyl; C1-C6 alkyl substituted with chlorine, fluorine, C1-C6 alkoxy, aryl, aryloxy, arylthio or C3-C8 cycloalkyl; C3-C8 cycloalkyl or aryl, with said reaction being carried out in a solvent in the presence of a base; wherein the useful diacid light-absorbing monomers have Formula III
Hxe2x80x94Yxe2x80x94Hxe2x80x83xe2x80x83III
wherein H represents an acidic hydrogen atom; Y is a divalent light-absorbing moiety selected from a variety of chromophoric classes including azo, disazo, bis-azo, methine, arylidene, polymethine, azo-methine, azamethine, anthraquinone, anthrapyridone (3H-dibenz[f,ij]isoquinoline-2,7-dione, nitroarylamines anthrapyridine (7H-dibenz[f,ij]isoquinoline-7-one, phthaloylphenothiazine (14H-naphth[2,3-a] phenothiazine-8,13-dione, benzanthrone(7H (de) anthracene-7-one), anthrapyrimidine(7H-benzo[e] perimidine-7-one), anthrapyrazole, anthraisothiazole, triphenodioxazine, thiaxanthene-9-one, fluorindine (5,12-dihydroquinoxaline[2,3-b]phenazine, quinophthalone, phthalocyanine, metal phthalocyanine, naphthalocyanine, metal naphthalocyanine, nickel dithiolenes, squarylium compounds, croconium compounds, coumarin (2H-1-benzopyran-2-one), coumarin imine (2H-1-benzopyran-2-imine), perinone, benzodifuran, phthaloylacridone, phthaloylphenoxazine (14H-naphtho[2,3-a]phenoxazine-8,13-done, phthaloylacridone (13H-naphtho[2,3-c]acridine-5,8,14-trione), anthraquinonethioxanthane (8H-naphtho[2,3-c]thioxanthene-5,8,13-trione, anthrapyridazone, pyrrolo[3,4-c]pyrrole, indigo, thioindigo, quinoline, xanthene, acridine, azine, cyanine, oxazine, 1,4 and 1,5-naphthoquinones, 2,5-diarylaminoterephthalic acids and esters, pyromellitic acid dimide, naphthalene-1,4,5,8-tetracarboxylic acid diimide, 3,4,9,10-perylene-tetracarboxylic acid diimide, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxopyrroline, arylisoindoline, hydroxybenzophenone, benoztriazole, naphthotriazole, diminoisoindoline, naphthopyran (3H-naphtho[2,1-6]pyran-3-one and 3-imine, phthalimides, 2-arylbenzazoles, carbostyryls, 1,2-diarylethenes, 2,5-diarylthiophenes, 2,5-diaryl-1,3,4-oxadiazoles, triazines, 2,5-diarylfurans, 2,5-diaryl-1,3,4-thiadiazoles, thiophenes, 1,3-diphenyl-2-pyrazolines, 2-arylbenzofurans, 2,6-diphenylbenzofurans, quinolines, quinoxalines, 3,4-diarylfuanones, distyrylarenes, benzanthrones, polyarenes and naphthalimides; wherein the hydrogen atoms of Formula III are independently bonded to an oxygen, sulfur, or nitrogen atom which is a part of the light absorbing moiety Y; wherein the useful non light-absorbing monomers have Formula IV,
Hxe2x80x94Y1xe2x80x94Hxe2x80x83xe2x80x83IV
wherein H represents an acidic hydrogen atom; Y1 is a divalent moiety, selected fromxe2x80x94O2Cxe2x80x94R1xe2x80x94CO2xe2x80x94 and xe2x80x94Oxe2x80x94R2xe2x80x94Oxe2x80x94 andxe2x80x94O2Cxe2x80x94R3xe2x80x94Oxe2x80x94, wherein R1 is selected from C2-C12 alkylene, 1-4-cyclohexylene, arylene, arylene-O-arylene, arylene-SO2-arylene, arylene-S-arylene, and C1-C4 alkylene-O-C1-C4 alkylene; wherein R2 is selected from arylene, arylene-O-arylene, arylene-S-arylene, arylene-SO2-arylene, phenylene-phenylene, and phenylene-C(R4)2-phenylene; wherein R4 is selected from hydrogen and C1-C4 alkyl; wherein R3 is selected from arylene.
In diacid light absorbing monomers having Formula III, the hydrogen atoms are preferably attached to an oxygen, a sulfur or a nitrogen atom which in combination provides two acidic functional group which can produce the corresponding anions under basic conditions by removal of the protons. The acidic functional groups usually have an acid dissociation constant of about 10xe2x88x921.5 to about 10xe2x88x9212 (pKa of from about 1.5 to about 12). In the case of nitrogen, both protons may be attached to a single nitrogen which is attached to a sulfonyl moiety thus providing two acidic hydrogens on a single functional group.
Typical, acidic groups which provide one acidic hydrogen includexe2x80x94CO2H, xe2x80x94SH, xe2x80x94OH attached to an aromatic ring, xe2x80x94CONHCOxe2x80x94, xe2x80x94SO2xe2x80x94NHxe2x80x94COxe2x80x94, xe2x80x94SO2xe2x80x94NHxe2x80x94SO2xe2x80x94, 1(H)-1,2,4-triazol-3-yl-, imidazolyl, benzimidazolyl, pyrazolyl, xe2x80x94SO2H attached to aromatic ring, xe2x80x94NHSO2R5 andxe2x80x94SO2NHR5, wherein R5 is selected from C1-C6 alkyl; C1-C6 alkyl substituted with at least one group selected from C1-C6 alkoxy, aryl, aryloxy, arylthio or C3-C8 cycloalkyl; C3-C8 cycloalkyl; aryl.
An example of an acidic functional group providing two acidic hydrogen attached to nitrogen is the sulfamoyl group (xe2x80x94SO2NH2).
The preferred method for producing light absorbing polymeric compositions utilizes the monomers of Formula III, wherein the protons are a part of thexe2x80x94CO2H, OH attached to aromatic ring, xe2x80x94COxe2x80x94NHxe2x80x94COxe2x80x94 or 1(H)-1,2,4-triazol-3-yl functional groups. The carboxy groups are normally attached to an aromatic ring carbon or aliphatic carbon which is a part of Y. The hydroxy groups are normally attached to an unsubstituted or substituted phenyl or naphthyl radical which is a part of Y. The xe2x80x94COxe2x80x94NHCOxe2x80x94 groups are usually attached to an aromatic ring to provide an imide such as phthalimide or naphthalimide which are a part of Y. The 1(H)-1,2,4-triazol-3-yl group has the following Formula V, wherein R5xe2x80x2 is 
selected from hydrogen, C1-C6 alkyl or aryl. It should be observed that the triazole may exist in isomeric form as follows: 
The 1(H)-1,2,4-triazol-3-yl group is preferably attached to a sulfur atom which is attached to the remainder of Y.
The method of the invention in the broadest sense involves the preparation of light absorbing polymeric compositions by reacting a diacidic monomer comprising at least 1 mole % of at least one diacidic light absorbing monomer represented by Hxe2x80x94Axe2x80x94H with an organic compound containing two reactive groups represented by Xxe2x80x94Bxe2x80x94X1, where B, X and X1 are as defined above. Thus, the method may be summarized as: 
The diacidic monomer Hxe2x80x94Axe2x80x94H must be acidic enough to form two nucleophiles in the presence of base under convenient reaction conditions for the most advantageous process. This usually requires that diacidic monomers have pKa values of about 12 or below.
The dinucleophilic monomer, formed by the removal of the two hydrogen atoms by the base, attacks the electrophilic compound II, thus displacing anions Xxe2x88x92 and X1xe2x88x92, with head-to-tail combination with covalent bonding to produce a linear polymer "Brketopenst"Axe2x80x94B"Brketclosest"n, wherein n represents the number of repeating units. The number of repeating units must be at least 2, but usually ranges between about 2 and about 25, with the preferred number being between about 3 and about 15.
The composition produced by the method of the invention comprises, as stated above, a polymer having the general formula "Brketopenst"Axe2x80x94B"Brketclosest"n. The composition also comprises one or more cyclic compounds having the general formula 
wherein m may be 1, 2, 3, or 4, e.g., the cyclic compounds having the general structures: 
The number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid Hxe2x80x94Axe2x80x94H, the structure of the organic compound Xxe2x80x94Bxe2x80x94X1, and the conditionss used to facilitate the reaction to produce the composition. The cyclic compounds may constitute up to about 35 weight percent, typically about 0.5 up to 30 weight percent, of the total weight of the composition produced by the method of the invention.
Suitable bases include alkali metal carbonates; alkali metal bicarbonates; tertiary amines such as triethylamine, tri-n-butylamine, N-methylpiperidine, N,Nxe2x80x2-dimethylpiperazine, N-methylmorpholine, N,N,Nxe2x80x2,Nxe2x80x2-tetramethylenediamine, etc.; aromatic nitrogen bases such as pyridines, picolines, quinolines, isoquinolines, N-alkylpyrroles, N-alkylimidazoles, etc.; bicyclic nitrogen containing bases having non-hindered electron pairs, such as 1,8-diazabicyclo[4,3,0]undec-7-ene (DBU), 1,5-diazabicylco[4,3,0]non-5-ene (DBN) and 1,4-diazadicyclo[2,2,2]octane (DABCO(copyright)).
Typical solvents useful in the polymerization reaction include aprotic polar solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, N-methyl-N-phenyl formamide, dimethyl sulfoxide, aliphatic nitrites, sulfolane, hexamethyl phosphoramide, etc. and mixtures thereof. Water, alcohols, ketones pyridine and ether-alcohols, such as the Cellosolves, also are sometimes useful. One requirement is that the solvent not form a stronger nucleophile in the presence of the base than that obtained from the diacidic monomer Hxe2x80x94Axe2x80x94H.
The new improved process of the invention allows the preparation of near ultraviolet (UV-A, UV-B and UV-C), visible and near infrared light absorbing linear polymeric compositions at relatively low temperatures, usually at from about 75xc2x0 C. to about 125xc2x0 C., without prolonged heating times. Furthermore, the method is adaptable to batch-process production which is advantageous for expensive products such as colorants, near infrared absorbers and near ultraviolet absorbers. The method is adaptable to a wide range of chromophoric classes since the polymer preparative reaction is carried out at relatively low temperature, which for example, allows colored polymeric compositions to be readily prepared from the very important azo class of colorants.
The preferred reactants of Formula II
Xxe2x80x94Bxe2x80x94X1 
are the disulfonate compounds where X and X1 are both a sulfonate ester of the formula xe2x80x94OSO2R, wherein R is selected from C1-C4 alkyl, phenyl or p-methylphenyl and wherein B is selected from C2-C6 alkylene, xe2x80x94CH2-1,4-cyclohexylene-CH2xe2x80x94, 2,2,4,4-tetramethyl-1,3-cyclobutylene, 1,4-cyclohexylene, xe2x80x94CH2CH2(OCH2CH2)2-3 and xe2x80x94CH2CH2O-1,4-phenylene-Oxe2x80x94CH2CH2xe2x80x94. Particularly, preferred reactants of Formula II are those where B is selected from xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH2CH(CH3)CH2xe2x80x94, xe2x80x94CH2C(CH3)2CH2xe2x80x94, xe2x80x94(CH2)4xe2x80x94, xe2x80x94(CH2)6xe2x80x94, xe2x80x94CH2CH2(OCH2CH2)1-4 and xe2x80x94CH2-1,4-cyclohexylene-CH2xe2x80x94.
Typical reactants of Formula II are as follows: 
The invention also relates to a light absorbing linear polymeric composition having Formula Ia: 
wherein A1 comprises the residue of at least one diacidic monomer having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and wherein B is defined above and which has been prepared by reacting a diacid light-absorbing monomer of Formula III (Hxe2x80x94Yxe2x80x94H) as defined above with an organic compound having Formula II (Xxe2x80x94Bxe2x80x94X1) as defined above, with the polymer producing reaction having been carried out in a solvent in the presence of base. The above-described light absorbing composition of formula Ia also contains or comprises one or more cyclic compounds having the formula 
wherein A1 and B are defined above and m may be 1, 2, 3, or 4. As stated hereinabove, the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid Hxe2x80x94Axe2x80x94H, the structure of the organic compound Xxe2x80x94Bxe2x80x94X1, and the conditions used to facilitate the reaction to produce the composition. The cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
The invention also relates to a light absorbing linear polymeric composition having Formula Ib 
wherein A2 comprises the residue of at least one diacidic monomer, having a light absorption maximum between about 300 nm and about 1200 nm, preferably between about 325 nm and 1100 nm and most preferably between about 350 nm and 1000 nm and which comprises at least about 50% by weight of the total of the composition of Formula Ib and wherein the remainder of A2 comprises the residue of at least one non-light absorbing monomer of Formula IV above, and wherein said polymeric composition has been prepared by reacting diacidic monomers of Formula III and Formula IV with an organic compound having Formula II above, with the polymer producing reaction having been carried out in a solvent in the presence of base. The light absorbing composition of formula Ib also contains or comprises one or more cyclic compounds having the formula 
wherein A2 and B are defined above and m may be 1, 2, 3, or 4. Again, the number and concentrations of the cyclic compounds is dependent upon a variety of factors such as the structure of diacid Hxe2x80x94Axe2x80x94H, the structure of the organic compound Xxe2x80x94Bxe2x80x94X1, and the conditions used to facilitate the reaction to produce the composition. The cyclic compounds of formula I-B may constitute up to about 35 weight percent, typically about 1 up 30 weight percent, of the total weight of the above-described light absorbing composition.
The polymer compositions of Formula I, Ia, and Ib and the cyclic compositions of formulas I-A, I-B and I-C are referred to as xe2x80x9cpolydyesxe2x80x9d herein when they absorb visible light thus rendering them strongly colored.
The invention further relates to a thermoplastic polymeric composition which comprises a thermoplastic polymer blended with at least one light absorbing linear polymeric composition of Formula I, Ia or Ib above which, as noted above, contain or comprise one or more cyclic compounds having the general formula I-A. The thermoplastic polymeric composition is usually selected from polyesters, polyolefins, polyamides, polyimides, polyvinyl chloride, polyurethanes, polycarbonates, cellulose esters, polyacrylates, polyvinylesters, polyester-amides, polystyrene, polyacrylonitrile-butadiene-styrene and polystyrene-acrylonitrile. The preferred thermoplastic polymeric composition comprises the light-absorbing polymeric compositions of Formula Ia.
The invention also relates to some of the diacidic light absorbing monomers used to prepare the light absorbing polymeric composition of Formula I, Ia, or Ib.
Preferred azo compounds useful in the practice of the invention correspond to Formula VI
R6xe2x80x94Nxe2x95x90Nxe2x80x94Zxe2x80x83xe2x80x83VI
wherein R6 is the residue of an aromatic or heteroaromatic amine which has been dizaotized and coupled with a coupling component Hxe2x80x94Z and is preferably derived from the aromatic and heteroaromatic amine classes of aniline, 1-aminonaphthalene, 1-aminoanthraquinone, 4-aminoazobenzene, 2-aminothiazole, 2-aminobenzothiazole, 3-amino-2,1-benzisothiazole, 2-aminothieno[2,3-d]thiazole, 5-aminoisothiazole, 5-aminopyrazole, 4-aminopyrazoloisothiazole, 2-amino-1,3,4-thiadiazole, 5-amino-1,2,4-thiadiazole, 5-amino-1,2,3-triazole, 2-amino-1,3,4-triazole, 2(5) aminoimidazole, 3-aminopyridine, 2(3) aminothiophene, 2(3) aminobenzo[b]thiophene, 2-aminothieno[3,2-b]thiophene, 3-aminothieno[2,3-c]isothiazole, 3-amino-7-benz-2,1-isothiazole, 3-aminobenzothienoisothiazole, 3-aminoisothiazole[3,4-d]pyrimidine, 5-amino-1,2,3-triazole, 3(4) aminophthalimide and 5(6) amino-1,2-benzisothiazolon-1,1-dioxide with said aromatic and heteroaromatic ring systems being unsubstituted or substituted with one or more groups selected from C1-C10 alkyl, C1-C6 alkoxy, C3-C8 cycloalkyl, carboxy, halogen, C1-C6 alkoxycarbonyl, formyl, C1-C6 alkanoyl, C1-C6 alkanoyloxy, dicyanovinyl, C3-C8-cycloalkanoyl, thiocyano, trifluroacetyl, cyano, carbamoyl, xe2x80x94CONH C1-C6 alkyl, CONHaryl, CON(C1-C6 alkyl)2, sulfamoyl, SO2NH C1-C6 alkyl, SO2N(C1-C6 alkyl)2, SO2NHaryl, SO2NH C3-C8 cycloalkyl, CONH C3-C8 cycloalkyl, aryl, aroyl, xe2x80x94NHSO2 C1-C6 alkyl, xe2x80x94N(C1-C6 alkyl)SO2 C1-C6 alkyl, xe2x80x94NHSO2 aryl, NHCO C1-C6 alkyl, NHCO C3-C8 cycloalkyl, NHCOaryl, NHCO2 C1-C6 alkyl, NHCONH C1-C6 alkyl, NHCONHaryl, N(C1-C6 alkyl)aryl, arylazo, heteroaryl, aryloxy, arylthio, C3-C8 cycloalkoxy, heteroarylazo, heteroarylthio, arylsulfonyl, tricyanovinyl, aryloxysulfonyl, C1-C6 alkylsulfonyl, trifluoromethyl, fluorosulfonyl, trifluoromethylsulfonyl, thiocyano, hydroxy, nitro or CHxe2x95x90D, wherein D is the residue of an active methylene compound as defined below.
Z is the residue of an electron rich coupling component selected from the classes of anilines, 1-aminonaphthalenes, 1,2-dihydroquinolines, 1,2,3,4-teterahydroquinolines, benzmorpholines (3,4-dihydro-2H-1,4-benzoxazine), pyrazolones, pyrazoles, 3-cyano-6-hydroxy-2-pyridones, 2,3-dihydroindoles, indoles, 4-hydroxycoumarins, 4-hydroxy-2-quinolones, imidazo[2,1-b]thiazoles, julolidines (2,3,6,7-tetrahydro-1H, 5H-benzo[ij]quinolizines), 1-oxajulolidines, 1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolines, 2,6-diamino-3 cyanopyridines, 2-aminothiazoles, 2-aminothiophenes, 5,5-dimethyl-1,3-cyclohexanedione (dimedone), phenols, naphthols, 2,4-pentanediones or acetoacetarylides; with the proviso that the compounds of Formula VI contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl group (xe2x80x94SO2NH2) which contains two acidic hydrogens.
Preferred disazo compounds correspond to Formula VII
R6xe2x80x94Nxe2x95x90Nxe2x80x94R7Nxe2x95x90Nxe2x80x94Zxe2x80x83xe2x80x83VII
wherein R6 and Z are as defined above and R7 is a divalent aromatic or heteroaromatic radical selected from the classes 1,4-phenylene, naphthalene-1,4-diyl, thiazol-2,5-diyl and thiophene-2,5-diyl: 
wherein R8 is selected from hydrogen or 1-2 groups selected from C1-C6 alkyl, C1-C6 alkoxy, cyano, halogen, xe2x80x94NHCO C1-C6 alkyl, xe2x80x94NHCO2 C1-C6 alkyl, xe2x80x94NHCO aryl, xe2x80x94NHCONH aryl or NHCONH C1-C6 alkyl; R9 is selected from hydrogen, C1-C6 alkyl, halogen, aryl, heteroaryl; R10 is selected from hydrogen, C1-C6 alkoxycarbonyl, cyano, carbamoyl, aryl, arylsulfonyl,aroyl, xe2x80x94CONH C1-C6 alkyl, or C1-C6 alkylsulfonyl; with the provision that two acidic functional groups containing one acidic hydrogen each or one functional group containing two acidic hydrogens are present on compounds of Formula VII.
The preferred methine, arylidene, polymethine, azamethine, 3-aryl-2,5-dioxypyrroline, 3-aryl-5-dicyanomethylene-2-oxopyrroline and aryl isoindoline compounds correspond to Formula VIII, VIIIa, VIIIb, IX, X, XI and XII, respectively: 
wherein R11 is the residue of an aniline, 1-naphthylamine, 1,2-dihydroquinoline, 1,2,3,4-tetrahydroquinoline, 1,3,3-trimethyl-2-methyleneindole, 1,3-dihydro-2-methylene-1,1,3-trimethyl-2H-benz[e]indole, imidazo [2,1-b] thiazole, benzomorpholine (3,4-dihydro-2H-1,4, benzoxazine), indole, 2,3-dihydroindole, 2-aminothiazole, julolidine (2,3,6,7-tetrahydro-1H, 5H-benz [ij] quinolizine, 1-oxajulolidine, 4H-pyrrolo [3,2,1-ij]-quinoline, phenol, naphthol, thiophenol, pyrrole, pyrazole, furan, thiophene, carbazole, phenothiazine or phenoxazine compound; R12 is selected from hydrogen, C1-C10 alkyl, C3-C8 alkenyl, C3-C8-alkynyl, C3-C8 cycloalkyl, aryl, (xe2x80x94CH2CH2Oxe2x80x94) 1-3 R13 and C1-C4 alkylene-C3-C8 cycloalkylene, wherein the C1-C6 alkyl groups may be substituted by at least one group selected from carboxy, C1-C6 carbalkoxy, C1-C6 alkanoyloxy, cyano, hydroxy, chlorine, fluorine, C1-C6 alkoxy, C3-C8 cycloalkyl or aryl; R13 is selected from hydrogen, C1-C6 alkoxy or C1-C6 alkanoyloxy; wherein D is the residue of an active methylene compound selected from malononitrile, -cyanoacetic acid esters, malonic acid esters, -cyanacetic acid amides, xe2x80x94C1-C6 alkylsulfonylacetonitriles, -arylsulfonylacetonitriles, xe2x80x94C1-C6 alkanoylacetonitriles, -aroylacetonitriles, -heteroarylacetonitriles, bis(heteroaryl)methanes, 1,3-indanediones, 2-furanones, benzo-2-furanones, naphtho-2-furanones, 2-indolones, 3-cyano-1,6-dihydro-4-methyl-2,6-dioxy (2H)-pyridines, benzo (b) thieno-3-ylidene propane dinitrile-5,5-dioxides, 1,3-bis (dicyanomethylene) indanes, barbituric acid, 5-pyrazolones, dimedone, 3-oxo-2,3-dihydro-1-benzothiophene-1,1-dioxides or aryl-C(CH3)Cxe2x95x90C(CN)2, with the proviso that two acidic functional groups containing one acidic hydrogen each, or a functional group containing two acidic hydrogens are present in compounds of Formula VIII, VIIIa, VIIIb, IX, X, XI, and XII.
Preferred azo-methine compounds correspond to Formula XIII
Dxe2x95x90HCxe2x80x94R7xe2x80x94Nxe2x95x90Nxe2x80x94Zxe2x80x83xe2x80x83XIII
wherein D, R7 and Z are as defined previously. The bis-azo compound corresponds to Formula VIIa
R6xe2x80x94Nxe2x95x90Nxe2x80x94Y1Nxe2x95x90Nxe2x80x94R6xe2x80x83xe2x80x83VIIa
wherein R6 is as defined above and Y1 is the residue of a bis coupling component selected from the classes of anilines, 1,2-dihydroquinolines, 1,2,3,4-tetrahydroquinolines, benzomorpholines (3,4-dihydro-2H-1, 4-benzoxazines), 3-cyano-6-hydroxy-2-pyridones, 2,6-diaminopyridines, 2,3-dihydroindoles, naphthylamines, 2-aminothiazoles, or a combination of these; with the provision the compounds of Formula VIIa contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl group (xe2x80x94SO2NH2) which contains two acidic hydrogens.
Several diacid monomers which are described in U.S. Pat. Nos. 4,804,719 and 3,689,501 are useful in the practice of the invention, including various anthraquinones, anthrapyridones, anthraisothiazoles, anthrapyrimidines, anthrapyrimidones, phthaloylacridones, etc.
Some of the preferred anthraquinone, anthrapyridone and anthrapyrimidine compounds correspond to the light absorbing compounds of Formulae XIV-XIXf 
wherein R14 is selected from the group consisting of hydrogen, 1-4 groups selected from amino, C1-C10 alkylamino, C3-C8 alkenylamino, C3-C8 alkynylamino, C3-C8 cycloalkylamino, arylamino, halogen, C1-C6 alkoxy, C1-C6 alkylthio, aryl, aroyl, C1-C6 alkanoyl, C1-C6 alkanoyloxy, NHCO C1-C6 alkyl, NHCOaryl, NHCO2 C1-C6 alkyl, NHSO2 C1-C6 alkyl, NHSO2 aryl, C1-C6 alkoxycarbonyl, aryloxy, arylthio, heteroarylthio, cyano, nitro, trifluoromethyl, thiocyano, SO2C1-C6 alkyl, SO2 aryl, xe2x80x94SO2NH C1-C6 alkyl, xe2x80x94SO2N(C1-C6 alkyl)2, xe2x80x94SO2N(C1-C6 alkyl) aryl, CONH C1-C6 alkyl, CON(C1-C6 alkyl)2, CON(C1-C6 alkyl) aryl, C1-C6 alkyl, furfurylamino, tetrahydrofurfurylamino, 4-(hydroxymethyl) cyclohexanemethylamino, 
or hydroxy; Q and Qxe2x80x2 are independently selected from xe2x80x94Oxe2x80x94, xe2x80x94N(COR10)xe2x80x94, xe2x80x94N(SO2R10)xe2x80x94, xe2x80x94N(R10)xe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94CO2xe2x80x94, xe2x80x94CON(R10)xe2x80x94, SO2N (R10)xe2x80x94, wherein R10 is selected from hydrogen, aryl, C3-C8 cycloalkyl, or C1-C10 alkyl; R15 is selected from hydrogen, cyano, C1-C6 alkylamino, C1-C6 alkoxy, halogen, arylthio, aryl, heteroaryl, heteroarylthio, C1-C6 alkoxycarbonyl, aroyl or arylsulfonyl; R16 is selected from hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl and aryl; R16 is selected from the group consisting of hydrogen, one or two groups selected from C1-C6 alkyl, halogen and C1-C6 alkoxy; wherein each C1-C6 alkyl group and C1-C6 alkyl group which is a portion of another group may contain at least one substituent selected from hydroxy, cyano, chlorine, fluorine, C1-C6 alkoxy, C3-C8 cycloalkoxy, C1-C6 alkylcyclohexyl, hydroxmethyl cyclohexyl, aryl and heteroaryl; with the provision that two acidic groups containing one acidic proton each or one acidic group containing two acidic hydrogens be present in the compounds of Formula XIV-XIXf.
Typical coupler residues which are represented by Z above in Formulae VI, VII, XIII for the classes of azo, disazo and azo-methine compounds, respectively include: 
wherein R17 is selected from the group consisting of hydrogen, 1-2 groups selected from C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylthio, xe2x80x94Oxe2x80x94C2-C6 alkylene-OH, Oxe2x80x94C2-C6 alkylene-C1-C6 alkanoyloxy, C1-C6 alkylene-OH, C1-C6 alkylene-C1-C6 alkanoyloxy, halogen, carboxy, C1-C6 alkoxycarbonyl, trifluoromethyl, NHCOR24, NHCO2R24, NHCON(R24)R25, and NHSO2R25, wherein R24 is selected from hydrogen, C1-C10 alkyl, C3-C8 cycloalkyl or aryl, R25 is selected from C1-C10 alkyl, C3-C8 cycloalkyl or aryl wherein each C1-C10 alkyl group in R24 and R25 may be further substituted with one or more groups selected from C3-C8 cycloalkyl, aryl, aryloxy, arylthio, CO2H, CO2 C1-C6 alkyl, cyano, hydroxy, succinimido, C1-C6 alkoxy, 
wherein R5xe2x80x2, R16xe2x80x2 and Q are as defined above; R18 and R19 are independently selected from hydrogen, unsubstituted C1-C10 alkyl, substituted C1-C10 alkyl, C3-C8 cycloalkyl, C3-C8 alkenyl, C3-C8 alkynyl and aryl or R18 and R19 may be combined with another element to which they are attached to form a radical Z having the formula 
wherein Q2 is selected from a covalent bond, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94CO2xe2x80x94, xe2x80x94Nxe2x80x94(C1-C6 alkyl)xe2x80x94, xe2x80x94N(CO C1-C6 alkyl)-, xe2x80x94N(SO2 C1-C6 alkyl)-, xe2x80x94N(CO aryl)-, or xe2x80x94N(SO2 aryl); R20, R21 and R22 are independently selected from the group consisting of or C1-C6 alkyl; R23 is selected from hydrogen, C1-C6 alkyl, C3-C8 cycloalkyl, heteroaryl or aryl.
Typical electron, rich aromatic residues which are represented by R11 in Formulae VIII-XII include: 
wherein R26 is selected from the group consisting of hydrogen, a group selected from C1-C6 alkoxycarbonyl, CO2H, C1-C6 alkyl or C1-C6 alkoxy; wherein R17-R23 are as defined previously.
Preferred coumarin compounds useful in the practice of the invention correspond to the following formulae: 
wherein Z3 is selected from cyano, C1-C6 alkoxycarbonyl, C1-C6 alkylsulfonyl, arylsulfonyl, aryl, heteroaryl, formyl, aroyl, C1-C6 alkanoyl or xe2x80x94CHxe2x95x90D, wherein D, R17, R18 and R19 are as defined previously with the provision that the coumarin compounds contain two acidic functional groups containing one acidic hydrogen each or contain one sulfamoyl (xe2x80x94SO2NH2) group which contains two acidic hydrogens.
Typical coupler residues which are represented by Y1 in Formula VIIa above include those of the formula (Z1xe2x80x94L1xe2x80x94Z2) wherein Z1 and Z2 are independently selected from 
wherein L1 is bonded to the nitrogen atom of Z1 and Z2; wherein L1 is selected from C2-C12 alkylene, C3-C8 cycloalkylene, arylene, C1-C4 alkylene-C3-C8 cycloalkylene-C1-C4 alkylene, C1-C4 alkylene-arylene-C1-C4 alkylene, C2-C4 alkylene-O-arylene-Oxe2x80x94C2-C4 alkylene, xe2x80x94C2-C4 alkylene O1-3xe2x80x94C2-C4 alkylene, C2-C4 alkylene-Sxe2x80x94C2-C4 alkylene, C2-C4 alkylene-SO2-C2-C4 alkylene, C2-C4 alkylene-N(SO2 C1-C6 alkyl)-C2-C4 alkylene, C2-C4 alkylene-N(SO2 aryl)-C2-C4 alkylene, C2-C4 alkylene-OCO2-C2-C4 alkylene, C2-C4 alkylene-O2C-arylene-CO2-C2-C4 alkylene, C2-C4 alkylene-O2Cxe2x80x94C1-C12 alkylene-CO2-C2-C4 alkylene, C2-C4 alkylene-O2Cxe2x80x94C3-C8 cycloalkylene-CO2-C2-C4 alkylene, C2-C4 alkylene-NHCOxe2x80x94C2-C4 alkylene and C2-C4 alkylene-NHSO2-C2-C4 alkylene; wherein R17, R18, R20, R21, R22, and R23 are as defined previously.
In the above definitions it is intended that in the terms C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkoxycarbonyl, C1-C6 alkylthio, C1-C6 alkylsulfonyl, C1-C6 alkanoyl, xe2x80x94CONH C1-C6 alkyl, xe2x80x94SO2NH C1-C6 alkyl, xe2x80x94CON(C1-C6 alkyl)2, xe2x80x94SO2N(C1-C6 alkyl)2, xe2x80x94NHSO2 C1-C6 alkyl, xe2x80x94N(C1-C6 alkyl) SO2 C1-C6 alkyl, etc. unless otherwise stated that the C1-C6 alkyl portion of the group refers to a straight or branched chain alkyl group containing one to six carbon atoms and these substituted with one or more groups selected from carboxy, cyano, xe2x80x94SO2NH2, SO2NH C1-C6 alkyl, cyano, fluorine, chlorine, C1-C6 alkoxy, aryloxy, aryl, heteroaryl, arylthio, heteroarylthio, C3-C8-cycloalkyl, xe2x80x94O2C C1-C6 alkyl orxe2x80x94CO2 C1-C6 alkyl.
The terms C1-C4 alkylene, C2-C4 alkylene, C1-C6 alkylene, C2-C6 alkylene, and C2-C12 alkylene are used to refer to divalent aliphatic hydrocarbon radicals containing one to four carbon atoms, two to four carbon atoms one to six carbon atoms, two to six carbon atoms, or two to twelve carbon atoms, respectively, and these optionally substituted with one or more groups selected from C1-C6 alkoxy, hydroxy, xe2x80x94O2C C1-C6 alkyl, carboxy, CO2 C1-C6 alkyl, chlorine, fluorine, aryl or aryloxy.
The terms C3-C8 cycloalkyl and C3-C8 cycloalkylene are used to refer to fully saturated monovalent and divalent cycloaliphatic radicals, respectively, and these substituted by one or more C1-C6 alkyl groups.
The terms C3-C8 alkenyl and C3-C8 alkynyl are used to refer to straight or branched hydrocarbon radicals containing at least one double bond or at least one triple bond, respectively.
In the terms aryl, NH aryl, aryloxy, aroyl, arylthio, arylsulfonyl, aryloxysulfonyl, xe2x80x94N(SO2 aryl)-, xe2x80x94N(CO aryl)-, NHCO aryl, xe2x80x94NH CONH aryl, NHSO2, aryl, etc., the aryl portion of the group represents phenyl and naphthyl and these substituted with one or more groups selected fromxe2x80x94CO2H, C1-C6 alkyl, CO2 C1-C6 alkyl, SO2NH2, SO2NH C1-C6 alkyl, hydroxy, O C1-C6 alkyl, S C1-C6 alkyl, phenyl, O-arylene-CO2H, xe2x80x94S-arylene-CO2H, SO2 arylene-CO2H, halogen, NHSO2 C1-C6 alkyl, trifluoromethyl, NH CO C1-C6 alkyl, cyano, or 1(H)-1,2,4-triazol-3-ylthio.
The term arylene is used to represent 1,2-, 1,3-, and 1,4-phenylene and these optionally substituted with one or more groups mentioned above as possible substituents on the aryl radical.
The term xe2x80x9cheteroarylxe2x80x9d is used to describe a 5 or 6 membered heterocyclic aromatic ring containing one oxygen atom, and/or one sulfur atom, and/or up to three nitrogen atoms, said heterocyclic aryl ring optionally fused to one or two phenyl rings or another 5 or 6-membered heteroaryl ring. Examples of such ring systems include thienyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, thiatriazolyl, oxatriazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, thiazinyl, oxazinyl, triazinyl, thiadiazinyl, oxadiazinyl, dithiazinyl, dioxazinyl, oxathiazinyl, tetrazynyl, thiatriazinyl, oxatriazinyl, dithiadiazinyl, imidazolinyl, dihydropyrimidyl, tetrahydropyrimidyl, tetrazolo [1,5-b]-pyridazinyl and purinyl, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, and the like and those rings substituted with one or more substituents listed above in the definition of the term xe2x80x9carylxe2x80x9d.
The term halogen is used to refer to fluorine, chlorine, bromine and iodine.
In the above definitions the unsubstituted and substituted C1-C10 alkyl groups or portion of groups mentioned refer to fully saturated hydrocarbon radicals containing one to ten carbon atoms, either straight or branched chain, and such alkyl radicals substituted with one or more of the following: C3-C8 cycloalkyl, aryl, hydroxy, cyano, xe2x80x94Oxe2x80x94C2-C4 alkylene OH, xe2x80x94Oxe2x80x94C2-C4 alkylene O2 Cxe2x80x94C1-C6 alkyl, xe2x80x94Sxe2x80x94C2-C4 alkylene-OH, chlorine, fluorine, xe2x80x94Oxe2x80x94C1-C6 alkyl, xe2x80x94O-aryl, xe2x80x94SO2 aryl, xe2x80x94SO2-C1-C6 alkyl, 2-pyrrolidino, phthalimidino, phthalimido, succinimido, glutarimido, o-benzoic sulfimide, vinyl sulfonyl, xe2x80x94NHCO C1-C6 alkyl, NHCOH, xe2x80x94NHSO2-C1-C6 alkyl, NHSO2 aryl, xe2x80x94NHCO aryl, xe2x80x94NHxe2x80x94CO2-C1-C6 alkyl, xe2x80x94SO2NH2, xe2x80x94SO2xe2x80x94NHxe2x80x94C1-C6 alkyl, xe2x80x94SO2Nxe2x80x94(C1-C6 alkyl)2, xe2x80x94CO2xe2x80x94C1-C6 alkyl, CONH2, xe2x80x94CONHxe2x80x94C1-C6 alkyl, xe2x80x94CO2-aryl, xe2x80x94CON(C1-C6 alkyl)2, xe2x80x94CONH aryl, xe2x80x94CONH(C1-C6 alkyl) aryl, xe2x80x94SO2N(C1-C6 alkyl) aryl, xe2x80x94SO2xe2x80x94NHxe2x80x94C3-C8 cycloalkyl, xe2x80x94CONHxe2x80x94C3-C8 cycloalkyl, xe2x80x94OCO2-C1-C6 alkyl, xe2x80x94O C2-C4 alkylene CN; groups of the formulae: 
wherein Y2 is selected from 1,2-phenylene; 1,2 pheylene substituted with C1-C6 alkyl, C1-C6 alkoxy, halogen, xe2x80x94CO2H, xe2x80x94CO2 C1-C5 alkyl or nitro; C2-C4 alkylene, vinylene, xe2x80x94O CH2xe2x80x94, xe2x80x94SCH2xe2x80x94, xe2x80x94CH2OCH2xe2x80x94, xe2x80x94OCH2CH2xe2x80x94, xe2x80x94CH2SCH2xe2x80x94, xe2x80x94NHCH2xe2x80x94, xe2x80x94NHCH2CH2, xe2x80x94N(C1-C6 alkyl)CH2xe2x80x94, NHC(C1-C6 alkyl)2, xe2x80x94N(C1-C6 alkyl) CH2CH2 or xe2x80x94NHC (aryl)2xe2x80x94; groups of the formulae:
xe2x80x94SR25, xe2x80x94SO2CH2CH2SR25, xe2x80x94OCH2CH2SR25, 
wherein R26 is selected from hydrogen, C1-C10 alkyl, C2-C4 alkylene-OH, C2-C4 alkylene-CO2H, C2-C4 alkylene-CO2 C1-C6 alkyl, chloro, C1-C6 alkoxy, C1-C4 alkylene-arylene-CO2H, C2-C4 alkylene-O-arylene-CO2H or C2-C4 alkylene-S-arylene-CO2H and R5xe2x80x2 R17, R25 and Q are as defined previously:
The term xe2x80x9clight absorbingxe2x80x9d is used to indicate the property of absorbing near ultra violet, visible or near infrared light, more particularly absorbing light between the wavelengths of 300-1200 nm, preferably between about 325 nm and 1100 nm, and most preferably between about 325 nm and 1000 nm.
Typical aromatic amines which are useful as the coupling components to prepare compounds of Formulae VI, VII and VIII and as intermediates for preparing the compounds of Formula VIII, VIIIa, IX, X, XI and XII are as follows: 
wherein Q, R5xe2x80x2, R17, R18, R19, R20, R21, R22 and R23 are as defined previously.
Typical diazotizable amines (R6 NH2) useful in the preparation of azo, disazo and bis-azo compounds of Formulae VI, VII, and VIIa, respectively, are adequately disclosed in the literature, e.g.:
M. Weaver and L. Shuttleworth, Dyes and Pigments, 3 (1982) 81-121;
L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107-63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.;
U.S. Pat. Nos. 3,438,961; 3,573,273; 3,639,384; 3,707,532; 3,790,557; 3,816,388; 3,816,392; 3,878,189; 3,980,634; 4,012,372; 4,039,522; 4,049,643; 4,083,684; 4,083,844; 4,097,475; 4,105,655; 4,119,621; 4,140,683; 4,180,503; 4,189,428; 4,207,233; 4,211,696; 4,264,495; 4,283,332; 4,400,318; 4,431,585; 4,456,551; 4,487,719; 4,542,207; 4,564,673; 4,619,991; 4,621,136; 4,650,861; 4,668,775; 4,734,490; 4,751,288; 4,760,133; 4,764,600; 4,837,269; 4,841,036; 4,843,153; 4,888,432; 4,960,874; 5,037,966; 5,132,411; 5,144,015; 5,283,326; 5,296,325; 5,352,774.
Typical coupling components Hxe2x80x94Z useful in preparing azo compounds, disazo and azo-methine compounds of Formula VI, VII and XIII, respectively, are disclosed in the literature, e.g: H. R. Schwander, Dyes and Pigments, 3(1982) 133-160; L. Shuttleworth and M. Weaver, Chem. Appl. Dyes, 1990, 107-63, edited by D. Waring and G. Hallas, Plenum, New York, N.Y.; U.S. Pat. Nos. 3,639,384; 3,639,385; 3,657,215; 3,673,169; 3,816,388; 3,829,410; 3,919,188; 3,950,130; 3,980,634; 4,041,025; 4,097,475; 4,119,621; 4,179,435; 4,234,482; 4,283,332; 4,341,700; 4,400,318; 4,431,585; 4,396,547; 4,619,992; 4,642,339; 4,650,861; 4,668,775; 4,764,600; 4,837,269; 4,843,153; 5,235,047; 5,283,326; 5,352,774.
Typical active methylene compounds useful in the preparation of methine, arylidene, polymethine, azamethine and azo-methine compounds corresponding to Formulae VIII, VIIIa, VIIIb, IX and XIII, respectively, are disclosed in the literature, e.g. U.S. Pat. Nos. 4,338,247; 4,617,373; 4,617,374; 4,707,537; 4,749,774; 4,826,903; 4,845,187; 4,950,732; 4,981,516 and 5,283,326.
According to the present invention the light-absorbing polymeric and cyclic compositions are incorporated into a wide variety of thermoplastic polymers using conventional techniques, e.g. solution or melt blending, such as those employed to incorporate other additives in such polymers (see R. Gachter and H. Mueller, Editors: Plastics Additives Handbook, Hansu Publishers, New York, 1985, pp. 507-533; 729-741). For example, the light absorbing polymeric and cyclic compositions may be dry blended in the form of pellets or powders with or without adhesion promoters or dispersing agents. This premix can be subsequently processed on extruders or injection molding machines. Other conventional additives such as plasticizers, nucleating agents, flame retardants, lubricants, etc. may also be present in the final thermoplastic composition.
A wide range of thermoplastic polymers useful for blending with the light absorbing polymeric and cyclic compositions are known in the art and includes the homopolymers, copolymers and blends of polyesters, e.g., poly(ethylene terephthalate); polyolefins, e.g., polypropylene, polyethylene, linear low density polyethylene, polybutylene, and copolymers made from ethylene, propylene and/or butylene; copolymers from acrylonitrile, butadiene, and styrene; copolymers from styrene and acrylonitrile; polyamides, e.g., Nylon 6 and Nylon 66; polyvinyl chloride; polyurethanes; polyvinylidene chloride; polycarbonates; cellulose esters, e.g., cellulose acetate, propionate, butyrate, or mixed esters; polyacrylates, e.g., poly(methyl methacrylate); polyimides; polyester-amides; polystyrene; and mixtures or blends thereof etc.
It should also be appreciated that a multiplicity of colors may be obtained by combining individual colors, e.g., subtractive colors such as yellow, magenta and cyan according to known color technology (see N. Ohta, Photographic Science and Engineering. Volume 15, No. 5, September--October 1971, pp. 395-415).
The particular chromophore groups present will, of course, determine the color (hue+value+chroma) of the colored polymer composition and finally the color (hue+value+chroma) of the thermoplastic polymer blends of the present invention. A large gamut of colors may be obtained, as noted above.
The actual amount of the light absorbing polymers used in combination with thermoplastic polymer will depend upon the inherent tinctorial strength of the chromophore used to prepare the light absorbing polymer, the mole % of the light absorbing monomer used to prepare the light absorbing polymer and the required level of light absorption necessary to achieve a certain property. Typically, the amount of light-absorbing polymer added to the thermoplastic polymer is such that the total amount of light-absorbing polymer in the final thermoplastic blend is from about 0.001% by weight to about 20% by weight, preferably from about 0.01% by weight to about 10% by weight. The final thermoplastic polymer blends thus provided are useful as a variety of molded and extruded articles, including thick and thin plastic films, plastic sheeting, molded plastic articles, containers and fibers, and the like.
When the light-absorbing polymeric compositions absorb visible light they may be used to impart light or heavy shades of a variety of colors to thermoplastics. Certain compounds which possess unique visible light-absorbing properties are useful also as toners in imparting a desirable neutral to slightly blue hue to polyesters having a yellow appearance as described in U.S. Pat. No. 5,384,377, which discloses the copolymerization of certain thermally stable colorants for this purpose during polyester manufacture. Some of the infra-red absorbing polymeric and cyclic compositions are useful in imparting invisible markings to thermoplastics as described in U.S. Pat. No. 5,461,136, wherein the infrared absorbing compounds are fluorescent in the near infrared and are copolymerized into the thermoplastic condensation polymer during manufacture. The ultra violet absorbing polymeric and cyclic compositions may be used to impart ultra violet (UV) light screening properties to the thermoplastics; to serve as optical brighteners for the thermoplastics or to serve as UV stabilizers for the polymers themselves or for other light absorbers such as colorants.
The weight average molecular weights (Mw) and the number average molecular weights (Mn) of the polymeric compositions were determined using gel permeation chromatography (GPC) analysis.
The following examples illustrate further the practice of the invention.